Emulsion and water-repellent composition

ABSTRACT

A composition having water-repellency at high temperature is provided. Some of the invention compositions also exhibits oil-repellency at high temperature. The composition comprises a fluorocarbon silane or hydrolyzate thereof; a surfactant; a polymerizable, silicon-containing compound; and a catalyst.

FIELD OF THE INVENTION

The present invention relates to an emulsion composition comprising afluorocarbon silane or hydrolyzate thereof and coated compositionproduced therefrom.

BACKGROUND OF THE INVENTION

Some silane-containing aqueous solutions that can providewater-repellent characteristics on the surface of a substrate have beendisclosed. See, e.g., U.S. Pat. Nos. 4,648,904, 4,757,106, 4,990,377,5,196,054, 5,550,184, and 5,664,014, European Patent 0 748 357, andJapanese Kokai Patent Application No. Hei 11(1999)-181355.

For example, U.S. Pat. No. 5,550,184 discloses reactive hydrolyzedsilane emulsions produced by emulsifying a hydrolyzable alkoxysilane inwater in the presence of a high HLB value emulsifier to simultaneouslyretain the hydrolyzable alkoxysilane in substantially totallyhydrolyzable state. The emulsion can produce durable coatings thatimpact water-repellent characteristics on a substrate.

Japanese Kokai Patent Application No. Hei 11(1999)-181355 discloses anemulsion containing a specific type of silane hydrolyzate, a specifictype of silicate a substance, and a surfactant. The emulsion, however,requires pH adjustments to alkaline region in order to exhibitwater-repellency and heat resistance characteristics.

Therefore, it is desirable to develop a new emulsion or coatingcontaining the emulsion that does not require the alkaline pH adjustmentto exhibit the desired heat-resistance and water-repellency properties.

Additionally, though these emulsions exhibit water-repellencycharacteristics, they do not exhibit oil-repellent property. Forexample, glass window of oven, range, or toaster can be coated with alayer formed by an emulsion having good water repellency at hightemperature, but it has a poor oil-stain resistance. Therefore, it isalso highly desirable to develop an emulsion that can exhibit bothwater-repellent and oil-repellent properties for a variety ofapplications.

Therefore, it is desirable to develop a new emulsion or coatingcontaining the emulsion that does not require the alkaline pHadjustment, or without the need of metal hydroxide or the chemicalsdisclosed above, to exhibit the desired heat-resistance andwater-repellency properties.

Additionally, though these emulsions exhibit water-repellencycharacteristics, they do not exhibit oil-repellent property. Forexample, glass window of oven, range, or toaster can be coated with alayer formed by an emulsion having good water repellency at hightemperature, but it has a poor oil-stain resistance. Therefore, it isalso highly desirable to develop an emulsion that can exhibit bothwater-repellent and oil-repellent properties for a variety ofapplications.

SUMMARY OF THE INVENTION

A composition comprises a fluorocarbon silane or hydrolyzate thereof; asurfactant; a polymerizable, silicon-containing compound; and acatalyst.

DETAILED DESCRIPTION OF THE INVENTION

The fluorocarbon silane generally contains at least one hydrolyzablefluorocarbon silane and can be represented byR_(f)—(CH₂)_(p)—Si{—(O—CH₂CH₂)_(n)—OR′}₃ where R_(f) can be one or moreC₃₋₁₈ perfluoroalkyl groups, each R′ can be the same or different and isindependently a C₁₋₃ alkyl groups or combinations thereof, p=2-4, andn=2-10). The preferred R_(f) is mixed perfluoroalkyl groups of 8 to 18carbons.

Examples of the fluorocarbon silanes include, but are not limited to,perfluoroalkylethyltris (2-(2-methoxyethoxy)ethoxy)silane when n is 2,and perfluoroalkylethyltris (2-(2-(2-methoxyethoxy)ethoxy)ethoxy)silanewhen n is 3, and combinations thereof. These fluorocarbon silanes areeither commercially available or can be produced by any means known toone skilled in the art as disclosed in Kir-Othmer Encyclopedia ofChemical Technology, 3^(rd) edition, vol. 20. For example, thefluorocarbon can be produced by the method disclosed in U.S. Pat. No.5,550,184, disclosure of which is incorporated herein by reference.

Any surfactant that can emulsify the hydrolysis product of thefluorocarbon silane can be used. The surfactant generally is asurfactant having an HLB value sufficiently high to inhibitself-condensation of the fluorocarbon silane hydrolysis product. Theterm “HLB” refers to the HLB system published by ICI America's, Inc.,Wilmington, Del.; Adamson, A. W., “Physical Chemistry of Surfaces”,4^(th) edition, John Wily & Sons, New York, 1982). The surfactant can beanionic, cationic, nonionic, amphoteric, or combinations thereof. Thepreferred surfactants are those with HLB values greater than 12, morepreferably greater than 16. Generally, the lower HLB value thesurfactant is, the larger amount of the surfactant is required tostabilize the emulsion. Two or more miscible surfactants generally canalso be combined or mixed for use as long as they are surfactants havingHLB values sufficiently high to inhibit self-condensation of thefluorocarbon silane hydrolysis products.

The HLB value of a nonionic surfactant can be determined by calculationwith a formula, among others, originated by Griffin of Atlas Co. (nowICI America) in the U.S. However, in the case of the anionic type or thecationic type, a method for determination by calculation of the HLBvalue is not available to date. Nevertheless, paying attention to thefact that changes in emulsification characteristics are sensitive tochanges in the HLB value, Atlas Company established and published amethod for the experimental determination of the HLB value by anemulsification experiment on standard oil. Companies other than Atlashave also established methods for experimental determination of HLBvalue. However, it can be clarified by the adoption of any experimentalmethod that the HLB value of the anionic type or the cationic type isgreater than 16.

Examples of nonionic surfactants include, but are not limited to,R′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H, othernonionic surfactants, and combinations thereof Examples of cationicsurfactants include, but are not limited toR′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻, other cationic surfactants, andcombinations thereof. Examples of anionic surfactants include, but arenot limited to, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺, C₁₂H₂₇—C₆H₄—SO₃ ⁻Na⁺, otheranionic surfactants, and combinations thereof. In each of the formulae,R_(f)′ is a perfluoroalkyl group generally having about 3-18 carbonatoms. The preferred surfactants are nonionic surfactants havingpolyethylene glycol in the molecular chain.

The content of the fluorocarbon silane in the water-based emulsion canbe about 0.1 weight % or higher, preferably about 2-20 weight %, andmost preferably 7-15 weight %, based on the total weight of theemulsion. The weight ratio of the fluorocarbon silane to the surfactantcan be in the range of from about 1:1 to about 10:1, preferably about10:2 to about 10:5, and even more preferably 10:3.

Any polymerizable, silicon-containing compound can be used so long as itcan copolymerize with the fluorocarbon silane hydrolysis product toimprove heat-resistant water-repellent characteristics, heat-resistantoil-repellent characteristics, or both. Suitable polymerizable,silicon-containing compounds include silicates, organosilanes, orcombinations thereof.

A suitable silicate can have the formula of Si—R₄ where R is one or moregroups selected from the group consisting of OCH₃, OCH₂CH₃,(OCH₂CH₂)_(m)OCH₃, and combinations thereof in which m=1-10, preferably1-3. Because a silicate represented by Si—((OCH₂CH₂)_(m)OCH₃)₄ (m=1-3)is water-soluble, it can dissolve in a water-based emulsion containing afluorocarbon silane hydrolysis product in a relatively short time, thesilicate represented by Si—((OCH₂CH₂)₂OCH₃)₄ is presently preferred.

The silicate to the fluorocarbon silane molar ratio can be in the rangeof from about 0.3:1 to about 10:1, preferably 0.3:1 to 5:1, and mostpreferably 0.4:1 to 2:1 Suitable organosilane includeorganoalkoxysilanes having the formula of R² _(q)Si(OR³)_(4-q) whereeach R² can be independently an alkyl group having 1 to about 10 carbonnumber; each R³ can be the same or different and each is independentlyan alkyl group having 1 to about 3 carbon number; and q=1-3. Examples ofsuitable organosilanes include, but are not limited to, methoxysilanes,ethoxysilanes, propoxysilanes, and combinations thereof.

The molar ratio of organoalkoxysilane to fluorocarbon silane can be inthe range of from about 0.3:1 to about 10:1, preferably 0.3:1 to 5:1,and most preferably 0.4:1 to 2:1.

The catalyst can be either an acid or a pH-adjusting agent. An aqueousacid such as phosphoric acid, boric acid, hydrochloric acid, sulfuricacid, nitric acid, acetic acid, oxalic acid, or combinations thereof canbe used as acid for the composition.

The presently preferred catalyst, if a silicate is used assilicon-containing compound, is phosphoric acid, boric acid, orcombinations thereof.

If an organosilane is used as the silicon-containing compound, theaqueous solution of the above-disclosed acid or aqueous alkalinesolution such as ammonia, pyridine, sodium hydroxide, or potassiumhydroxide, can be used as catalyst. Aqueous phosphoric acid solution isespecially suitable.

The amount of catalyst is generally an effective amount that can producean emulsion having the characteristics disclosed. It is also an amount,when a silicate is used, that can adjust the pH of the emulsion to 4.5or less, preferably less than 2.2 such as about 2.0 depending on thecatalyst. If an organosilane is used, there is no pH limitation.However, if a higher pH is desired, an aqueous alkali solution can beused to adjust the pH to 7.0 or more, especially 7.0-12.

The heat-resistant water-repellent characteristics of the coated layerproduced from the emulsion composition can be effectively improved byeither adjusting its pH to alkaline region or, if a silicate is used asthe silicon-containing compound, acidifying to acidic region using, forexample, phosphoric acid, boric acid, or combinations thereof.

The emulsion composition of the present invention can contain a pigment,a bactericide, an ultraviolet ray absorbent, an antioxidant, or othercustomarily used additives in a range without affecting the stability ofthe emulsion and the heat-resistant water-repellent characteristics ofthe coated layer.

Any methods known to one skilled in the art can be used for thepreparation of the emulsion composition of the present invention. Thecomponents can be combined in any order to produce the composition.

However, it is preferable to dissolve a surfactant in water followed byaddition of a fluorocarbon silane slowly, such that self-condensation ofthe fluorocarbon silane is inhibited and a hydrolyzed state of thefluorocarbon silane is maintained, with agitation such as stirring, anyadditives desired, the catalyst, and finally the polymerizable,silicon-containing compound. Generally the pH is not appreciablyaffected by the addition of the silicon-containing compound. Thisprocess can be best used to inhibit self-condensation and to maintain ahydrolyzed state of the fluorocarbon silane.

The water-based emulsion of the present invention can be coated with orto any substrate. The substrates are rendered water-repellent,oil-repellent, or both characteristics by coating the emulsion on thesubstrate surface followed by drying. Examples of suitable substratesinclude, but are limited to, aluminum, stainless steel, or other metalsheets, glass, glass sheet, ceramic tile, brick, concrete, stone, wood,masonry, fiber, leather, plastics, or other substrate that can be usedunder high temperature conditions. The coating of the water-basedemulsion on a substrate can be carried out by any methods known to oneskilled in the art such as, for example, dipping method, spray method,spin coating method, roll coating method, or other publicly knownmethods. The dipping method is preferred because it does not causedamage to transparency on a glass substrate.

Heating can also be carried out in order to accelerate the dryingprocess. In general, drying is carried out in a temperature range ofabout 100-350° C. for about 5 minutes to 24 hours.

Furthermore, before coating the water-based emulsion of the presentinvention on a substrate, a silicone compound such as, for example,silica, can be coated to form a base or backing layer. By coating theemulsion on top of this layer, the heat-resistant water-repellentcharacteristics can be maintained for an prolonged period. The substrateafter the coating with the emulsion composition, if necessary, can bewashed with water after it is dried to remove the residual surfactant.

EXAMPLES

The following examples are provided to illustrate the invention and arenot to be construed as to unduly limit the scope of the invention.

The components used in the following application examples andcomparative examples are as follows.

The fluorocarbon silane was a mixture of perfluoroalkyl silanesrepresented by R_(f) —(CH₂)₂—Si{—(O—CH₂CH₂)₂—OCH₃}₃, where R_(f) isF(k=6, 1-2 wt. %; K=8, 62-64 wt %; k=10, 23-30 wt %; and k=12-18, 2-6weight %). The surfactant was a nonionic surfactant represented byR_(f)′—CH₂ CH₂—O—(CH₂CH₂O)₁₁—H, where R_(f)′ is a perfluoroalkyl grouphaving 3-18 carbon atoms, obtained from E. I. de Nemours & Company,Wilmington, Del. The silicate wastetrakis[2—(2—methoxyethoxy)ethoxy]silicate (Si(DEGM)₄).Organoalkoxysilane with the following formula of (CH₃)Si(OCH₃)₃(organomethoxysilane) was used. These chemicals were obtained from KantoChemicals Co., Inc., Japan.

Application Example 1

The nonionic surfactant was dissolved in water so that its amount was 30parts by weight with respect to 100 parts by weight of the fluorocarbonsilane to produce a mixture. The fluorocarbon silane at 10 weight %based on the total weight of the water-based emulsion was slowly (2.1 kgwas added over a 30 minute period) added to the mixture while stirredusing a mechanical stirrer. Self-condensation of the fluorocarbon silanewas inhibited and the hydrolyzed state was maintained. While the pH ofthe emulsion was being measured with a pH meter, phosphoric acid wasadded. When the pH reached 2.0, the addition of the phosphoric acid wasstopped. Si(DEGM)₄ was added such that the molar fraction of theSi(DEGM)₄ with respect to the fluorocarbon silane was 0.45 to produce awater-based emulsion.

Then, after stirring the water-based emulsion for 2 to 4 hours, it wascoated on an aluminum sheet (JIS 1100 with 2.5 cm×5.0 cm, thickness 1mm) to yield a test specimen.

The water-based emulsion was coated by dip coating. Dip coating wasconducted by lowering the test specimen at a speed of 300 mm/min intothe water-based emulsion, maintaining it in such a state for 5 minutes,and pulling it up at a speed of 50 mm/min. Drying after coating wascarried out at 200° C. for 60 minutes in an oven.

A drop of pure water (2 μl) was placed on the coated layer surface ofthe test specimen. With a contact angle meter (Kyowa InterfacialScience, Japan), the contact angle was measured. The results are shownin Table 1.

The test specimen was placed in an oven at 375° C. After the time shownin Table 1 had elapsed, the contact angle was measured and is shown inTable 1.

Application Example 2

In Application Example 2, a water-based emulsion containing afluorocarbon silane hydrolysis product of the same composition as inApplication Example 1 was prepared except that boric acid was usedinstead of the phosphoric acid and the pH was 4.0. A test specimen wasprepared, and the same water-repellent test was carried out. The resultsfor contact angles are shown in Table 1.

Comparative Examples 1 through 5

In Comparative Examples 1 through 5, water-based emulsions containingwere prepared as in Application Example 1 except that hydrochloric acid,sulfuric acid, nitric acid, acetic acid, and formic acid were used,instead of the phosphoric acid, for adjusting the pH to 2.0. Testspecimens were prepared, and the same water-repellent tests were carriedout. The results are shown in Table 1.

Comparative Examples 6 through 9

In Comparative Examples 6 through 9, water-based emulsions were preparedas in Application Example 1 except that an aqueous ammonia solution,sodium hydroxide, potassium hydroxide, and pyridine were used (Table 1)instead of phosphoric acid for adjusting pH to 8-11. Test specimens wereprepared, and the same water-repellent tests were carried out. Theresults are shown in Table 1.

TABLE 1^(a) App 1 App 2 Com 1 Com 2 Com 3 Com 4 Com 5 Com 6 Com 7 Com 8Com 9 pH agent PA BA HA SA NA AA FA AH SH PH Py Final pH 2.0 4.0 2.0 2.02.0 2.0 2.0 10.8 11.2 11.0 8.1 IWRA 120 120 121 120 119 119 121 118 114115 120 WRA-15 125 112 8 15 8 18 8 120 114 108 118 WRA-20 — 100 — — — —— — — — — WRA-40 104 — — — — — — 97 98 81 95 ^(a)The abbreviations usedwere: App, Application Example; Com, Comparative Example; PA, phosphoricacid; HA, hydrochloric acid; BA, boric acid; HA, hydrochloric acid; AA,acetic acid; FA, formic acid; AH, aqueous ammonium hydroxide solution;SH, aqueous sodium hydroxide solution; PH, aqueous potassium hydroxidesolution; Py, pyridine; pH agent denotes an acid or base used foradjusting pH of the emulsion; Final pH denotes to the final pH of theemulsion; IWRP denotes initial water-repellent angle (degrees); WRA-15denotes water-repellent angle (degrees) after 15 hours at 375° C.;WRA-20 denotes water-repellent angle (degrees) after 20 hours at 375°C.; and WRA-40 denotes water-repellent angle (degrees) after 40 hours at375° C.

Comparing Application Examples 1-2 and Comparative Examples 1-5, coatedlayers having excellent water-repellent characteristics were obtainedfor all samples. However, when phosphoric acid or boric acid was used toadjust the emulsion to acidic region, the value of the water-repellentangle of the coated layer surface was about the same as, or higher than,that before aging after 15 hours at 375° C. This indicates that a coatedlayer had not only water-repellent characteristics alone but alsoheat-resistant, water-repellent characteristics.

Comparing Application Examples 1-2 and Comparative Examples 6-9, coatedlayers having excellent heat-resistant water-repellent characteristicswere obtained for those emulsions adjusted to acidic region or alkalineregion. However, the value of the water-repellent angle of the coatedlayer surface was more than 100° even after 20 or 40 hours at 375° C. ifphosphoric acid or boric acid were used. However, that those using analkali solution as catalyst had value lower than 100. In other words,the coated layers containing phosphoric acid or boric acid had betterdurability of heat-resistant water-repellent characteristics than thosecontaining an alkaline pH-adjusting agent. The results also show thatthe coated layer formed by coating the water-based emulsion of thepresent invention maintained excellent water-repellent characteristicseven under high temperature conditions for a prolonged period.

Application Examples 3-5

Surfactant (30 parts by weight for 100 parts by weight of fluorocarbonsilane) was dissolved in water. Fluorocarbon silane shown in Table 2 (10weight % for the entire weight of water emulsion) was slowly added whileusing a conventional stirring method for stirring to inhibitfluorocarbon silane from self-condensation and to maintain fluorocarbonsilane being hydrolyzed. While using a pH meter for measurement of thepH of the emulsion, an acid or pH-adjusting agent shown in Table 2 wasadded. The addition was stopped when a final pH shown in Table 2 wasobtained. (CH₃)Si(OCH₃)₃ was added to obtain molar ratio of(CH₃)Si(OCH₃)₃ to fluorocarbon silane of 0.45 to make a water emulsion.

After the water emulsion was stirred for 2-4 hours, it was applied ascoating on a glass plate (2.5 cm×5.0 cm, thickness: 3 mm) to make a testsample.

A dip-coating method was used for the water emulsion. The test samplewas dipped into the water emulsion at 300 mm/min, held for 5 minutes,and lifted up at 50 mm/min. After it was coated, it was dried at 200° C.for 60 minutes in an oven to prepare a test sample.

Purified water (2 μl) was dripped onto the surface of coated layer oftest sample. A contact angle was obtained by measurement using a contactangle meter (made by Kyowa Kaimen Kagaku, Japan). The results are shownin Table 2.

Chicken oil (10 mg) was sprayed onto the surface of the coated layer oftest sample, followed by baking at 250° C. for 60 minutes. The burnt oilstain was wiped off five times with gauze, followed by visualobservation to see how much burnt oil stain was removed. The results areshown in Table 2.

Comparative Examples 10-11

In Comparative Examples 10 and 11, water emulsion containingfluorocarbon silane hydrolyzate having the same composition as that ofwater emulsion obtained in Application Examples 3 and 4 was prepared anda test sample was made, except tetrakis(2-(2-methoxyethoxy) ethoxy)silicate (Si (DEGM)₄) was used. The same water-repellency test andoil-stain resistance test were performed. The results are shown in Table2.

Comparative Example 12

Both the same water-repellency test and same oil-stain resistance testperformed in Application Example 3 were performed in Comparative Example12. The results are shown in Table 2.

Comparative Examples 13-14

Water emulsion containing fluorocarbon silane hydrolyzate having thesame composition as that in Application Example 3 was prepared exceptthat no catalyst was used in Comparative Example 13 and that (Si(DEGM)₄)instead of organomethoxysilane was used. Water-repellency and oil-stainresistance tests were carried out. The results are shown in Table 2.

Water emulsion containing fluorocarbon silane hydrolyzate havingcomposition similar to that obtained in Application Example 3 wasprepared in Comparative Example 14 except that no catalyst was used.Water-repellency and oil-stain resistance tests were carried out. Theresults are shown in Table 2.

TABLE 2^(a) App 3 App 4 App 5 Com 10 Com 11 Com 12 Com 13 Comp 14 Si OMSOMS OMS SiD SiD — SiD₄ OMS PH agent PA HA Am PA HA — — — Final pH 2.02.0 10.8 2.0 2.0 — 5.0 5.0 Substrate Glass Glass Glass Glass Glass GlassGlass Glass PCA 120 120 119 120 119 121 119 118 DRBS Comp CompE Comp SRSR None SR SR ^(a)See footnotes in Table 1 for abbreviations. Those notshown in Table 1 are Si, type of silicon compound; OMS,Organomethoxysilane; SiD, Si(DEGM)₄; Am, ammonia; —, not present ormeasured; PCA, primary contact angle (degrees); and DRBS, degree forremoval of oil stains (Comp, satins were almost completely removed;CompE, satins were essentially completely removed; SR, stains remained;and none, no stains were removed).

In Application Example 3, very small amounts of oil remained on theglass surface, but all oil could be easily and almost completely removedby wiping. In Application Example 4, oil was more difficult to remove bywiping than Application Example 3, but essentially all of burnt oilstain could be removed. Stains could be easily and almost completelyremoved in Application Example 5.

No burnt oil stain could be removed by wiping the surface of glasscoated in Comparative Example 12. Oil was spread and remained on thesurface of glass in Comparative Examples 10, 11, and 13 obtained withproducts containing silicate. Oil was spread and remained in ComparativeExample 14 obtained with a product containing no pH-adjusting agent butorganomethoxysilane.

The results show that the surface of coated layers with compositionscontaining organomethoxysilane or silicate exhibited good waterrepellency. Oil-stain resistance was considerably improved by usingorganomethoxysilane to with either an acid or a pH-adjusting agent.Using phosphoric acid further improved oil-stain resistance.

Application Examples 6-7

A water emulsion was prepared the same as Application Example 3, andapplied as coating on a glass plate (2.5 cm×5.0 cm, thickness: 3 mm) toform a test sample.

Purified water (2 μl) was dripped on the surface of coated layer of testsample. A contact angle as obtained by measurement using a contact anglemeter (made by Kyowa Kaimen Kagaku, Japan). The results are shown inTable 3.

Each test sample was placed in an oven at 330° C., the contact angle wasmeasured similarly after 6 hours and after 10 hours aging. Results areshown in Table 3.

Comparative Examples 15-17

Each water emulsion was obtained in the same process used in ApplicationExample 3, except for replacing organomethoxysilane with a silicacompound shown in Table 3. It was applied as coating on a glass plate(2.5 cm×5.0 cm, thickness: 3 mm) to obtain each test sample on whichcontact angle was similarly measured as in Application Example 6.Results are shown in Table 3.

TABLE 3^(a) App 6 App 7 Com 15 Com 16 Com 17 Si OMS OMS EpS AS ECS pH PAHA PA PA PA Final pH 2.2 2.2 2.2 2.2 2.2 Substrate Glass Glass GlassGlass Glass PWRA 116 114 116 117 116 WRA-6 138 112 101 46 109 WRA-10 137113 73 33 97 ^(a)See Tables 1 or 2 for footnotes. Those not shown inTable 2 are: EpS, epoxysilane; AS, aminnosilane; ECS,epoxycyclohexylsilane; PWRA, primary water-repellency angle (degree);WRA-6, water-repellency angle (degree) after 6 hours at 330° C.; WRA-10,water-repellency angle (degree) after 10 hours at 330° C.

In Application Example 6, water-repellency angle on the surface ofcoated layer after 6 hours and after 10 hours at 330° C. was better thanthat before aging, indicating that a coated layer having good waterrepellency at high temperature was obtained.

In Comparative Examples 15-17, a similar primary water-repellency angleobtained in Application Example 6 was obtained by a silicon compoundother than organomethoxysilane, and that a coated layer having waterrepellency was obtained. However, each water-repellency angle after 10hours at 330° C. was reduced, even phosphoric acid was used, and nocoated layer had any water repellency at high temperature.

Application Example 7, in which water emulsion containingorganomethoxysilane was used as in Application Example 6, showed that acoated layer had good water repellency at high temperature even thoughhydrochloric acid was used as pH-adjusting agent.

Application Example 8

Water emulsion was prepared similar to Application Example 3 and wascoated on an aluminum plate (JIS1100 2.5 cm×5.0 cm, thickness: 1 mm) toobtain a test sample.

Purified water (2 μl) was dripped on the surface of coated layer of testsample. Contact angle was measured using a contact angle meter (made byKyowa Kaimen Kagaku, Japan). The results are shown in Table 4.

Each test sample was placed in an oven at 370° C. and after 40 hours,the contact angle was similarly measured. Results are shown in Table 4.

Comparative Examples 18-21

Each water emulsion was obtained the same as Application Example 3,except for using a silicon compound shown in Table 4. It was coated onan aluminum plate (JIS1100, 2.5 cm×5.0 cm, thickness: 1 mm) to obtaintest sample. A contact angle was measured as in Application Example 6.Results are shown in Table 4.

TABLE 4^(a) App 8 Com 18 Com 19 Com 20 Com 21 Si OMS SiD SiD SiD OMS pHagent PA HA PA AH — Final pH 2.2 2.2 2.2 10.8 5.0 Substrate AluminumAluminum Aluminum Aluminum Aluminum PWRA 120 117 120 112 118 WRA-40^(b)105 10 15 45 31 ^(a)See previous footnotes. ^(b)The temperature was 370°C.

Application Example 8 and Comparative Examples 18-21 had about the sameprimary water-repellency angles showing that each coated layer had goodwater repellency. However, Comparative Examples 18-20, in which silicatewas used, had significantly reduced water-repellency angle after 40hours at 370° C. while Application Example 8 had water repellency of 105degrees after 40 hours at 370° C. The results demonstrate that a coatedlayer having good water repellency at high temperature and gooddurability could be obtained using organomethoxysilane.

Comparative Example 21 had considerably reduced water-repellency angleafter 40 hours at 370° C., indicating that even with use oforganomethoxysilane, the lack of a catalyst failed to yield a goodwater-repellency at high temperature.

The above results show that a coated layer produced from water emulsionscontaining fluorocarbon silane or its hydrolyzate exhibits good waterrepellency at high temperature and good oil-stain resistance. A coatedproduct made by applying water emulsion of the present invention waseffective to remove oil stains easily, and can maintain good waterrepellency at high temperature.

What is claimed is:
 1. A composition comprising a fluorocarbon silane orhydrolyzate thereof; a surfactant; a polymerizable, silicon-containingcompound; and a catalyst wherein said fluorocarbon silane has theformula Of R_(f)—(CH₂)_(p)Si{—(O—CH₂CH₂)_(n)—OR′}₃, R_(f) is a C₃₋₁₈perfluoroalkyl group or combinations thereof, each R′ is independently aC₁₋₃ alkyl groups or combinations thereof, p is 2 to 4, inclusive, and nis 2 to 10, inclusive; said silicon-containing compound is selected fromthe group consisting of a silicate, an organosilane, and combinationsthereof; and said catalyst is phosphoric acid, boric acid, hydrochloricacid, nitric acid, acetic acid, oxalic acid, ammonia, pyridine, sodiumhydroxide, or potassium hydroxide, or combinations of two or morethereof if said silicon-containing compound is said organosilane orphosphoric acid, boric acid, or combinations thereof if saidsilicon-containing compound is said silicate.
 2. A composition accordingto claim 1 wherein said silicon-containing compound is said silicatehaving the formula of Si—R₄, R is selected from the group consisting ofOCH₃, OCH₂CH₃, (OCH₂CH₂)_(m)OCH₃, and combinations thereof, and m is 1to 10, inclusive; and said catalyst is said phosphoric acid, said boricacid, or combinations thereof.
 3. A composition according to claim 1wherein said fluorocarbon silane is selected from the group consistingof perfluoroalkylethyltris(2-(2-methoxyethoxy)ethoxy)silane,perfluoroalkylethyltris (2-(2-(2-methoxyethoxy)ethoxy)ethoxy)silane, andcombinations thereof.
 4. A composition according to claim 2 wherein saidfluorocarbon silane isperfluoroalkylethyltris(2-(2-methoxyethoxy)ethoxy)silane,perfluoroalkylethyltris(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)silane, orcombinations thereof.
 5. A composition according to claim 1 wherein saidsurfactant R′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ^(−NH) ₄ ⁺,C₁₂H₂₇—C₆H₄—SO₃—Na⁺, or combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 6. Acomposition according to claim 2 wherein said surfactantR′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄ 13 O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺,C₁₂H₂₇—C₆H₄—SO₃—Na⁺, or combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 7. Acomposition according to claim 3 wherein said surfactantR′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺,C₁₂H₂₇—C₆H₄—SO₃—Na⁺, or combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 8. Acomposition according to claim 4 wherein said surfactantR′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃₎ ₃ ⁺Cl⁻, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ^(−NH) ₄⁺, C₁₂H₂₇—C₆H₄—Na⁺, or combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 9. Acomposition according to claim 8 wherein said surfactant has a HLB valuegreater than
 12. 10. A composition according to claim 4 wherein saidsurfactant has a HLB value greater than
 16. 11. A composition accordingto claim 1 wherein said fluorocarbon silane isperfluoroalkylethyltris(2-(2-methoxyethoxy)ethoxy)silane,perfluoroalkylethyltris (2-(2-(2-methoxyethoxy)ethoxy)ethoxy)silane, orcombinations thereof; and said silicon-containing compound is saidsilicate having the formula of Si—R₄, R is selected from the groupconsisting of OCH₃, OCH₂CH₃, (OCH₂CH₂)_(m)OCH₃, and combinationsthereof, and m is 1 to 10, inclusive.
 12. A composition according toclaim 11 wherein said surfactant has a HLB value greater than
 16. 13. Acomposition according to claim 11 wherein said silicon-containingcompound is Si—((OCH₂CH₂)₂OCH₃)₄; and said surfactant is selected fromthe group consisting of R′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H,C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H, R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl³¹ ,C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺, C₁₂H₂₇—C₆H₄—SO₃—Na³⁰ , and combinationsthereof, and R_(f)′ is a perfluoroalkyl group having about 3 to about 18carbon atoms.
 14. A composition according to claim 1 wherein saidsilicon-containing compound is said organosilane having the formula ofR² _(q)Si(OR³)_(4-q), each R² is independently an alkyl group having 1to 10 carbon number, each R³ is independently an alkyl group having 1 toabout 3 carbon number, and q is 1 to 3, inclusive.
 15. A compositionaccording to claim 14 wherein said fluorocarbon silaneperfluoroalkylethyltris(2-(2 -methoxyethoxy)ethoxy)silane,perfluoroalkylethyltris (2-(2-(2-methoxyethoxy)ethoxy)ethoxy)silane, orcombinations thereof.
 16. A composition according to claim 15 whereinsaid surfactant has a HLB value greater than
 12. 17. A compositionaccording to claim 16 wherein said surfactant has a HLB value greaterthan
 16. 18. A composition according to claim 15 wherein said surfactantis selected from the group consisting of R′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H,C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H, R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ³⁰ Cl³¹ ,C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺, C₁₂H₂₇—C₆H₄—SO₃—Na⁺, and combinationsthereof, and R_(f)′ is a perfluoroalkyl group having about 3 to about 18carbon atoms.
 19. A composition according to claim 17 wherein saidsurfactant is selected from the group consisting ofR′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺,C₁₂H₂₇—C₆H₄—SO₃—Na⁺, and combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 20. Acomposition according to claim 14 wherein said silicon-containingcompound is organomethoxysilane; said surfactant has a HLB value greaterthan 12; and said surfactant is selected from the group consisting ofR′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻, C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺,C₁₂H₂₇—C₆H₄—SO₃—Na⁺, and combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 21. Acomposition according to claim 20 wherein said surfactant has a HLBvalue greater than
 16. 22. A process comprising contacting a substratesurface with a composition wherein said composition is as recited inclaim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,20, or 21, and said substrate is metal, glass, ceramic, tile, brick,concrete, wood, masonry, fiber, leather, plastics, or stone.
 23. Aprocess comprising dissolving a surfactant in water to produce asurfactant-water mixture; combining said surfactant-water mixture with afluorocarbon silane to produce a silane-surfactant mixture; combiningsaid silane-surfactant mixture with a catalyst to produce a pH-adjustedmixture; and combining said pH-adjusted mixture with polymerizable,silicon-containing compound to produce an emulsion wherein saidfluorocarbon silane has the formula ofR_(f)—(CH₂)_(p)—Si{—(O—CH₂CH₂)_(n)—OR′}₃, R_(f) is a C₃₋₁₈perfluoroalkyl group or combinations thereof, each R′ is independently aC₁₋₃ alkyl groups or combinations thereof, p is 2 to 4, inclusive, and nis 2 to 10, inclusive; said silicon-containing compound is selected fromthe group consisting of a silicate, an organosilane, and combinationsthereof; and said catalyst is phosphoric acid, boric acid, hydrochloricacid, nitric acid, acetic acid, oxalic acid, ammonia, pyridine, sodiumhydroxide, or potassium hydroxide, or combinations thereof if saidsilicon containing or phosphoric acid, boric acid, or combinationsthereof if said silicon-containing compound is said silicate.
 24. Aprocess according to claim 23 wherein said surfactant has a HLB valuesgreater than
 16. 25. A process according to claim 25 wherein saidsurfactant is selected from the group consisting ofR′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H, C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H,R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl³¹ , C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺,C₁₂H₂₇—C₆H₄—SO₃—Na⁺, and combinations thereof, and R_(f)′ is aperfluoroalkyl group having about 3 to about 18 carbon atoms.
 26. Aprocess according to claim 23 wherein said silicon-containing compoundis Si—((OCH₂CH₂)₂OCH₃)₄; said surfactant has a HLB values greater than12; and said surfactant is R′_(f)—CH₂CH₂—O—(CH₂CH₂O)₁₁—H,C₉H₁₉—C₆H₄—O—(CH₂CH₂O)₅₀—H, R′_(f)—CH₂CH₂SCH₂CH(OH)CH₂N(CH₃)₃ ⁺Cl⁻,C₁₂H₂₅(OCH₂CH₂)₄OSO₃ ⁻NH₄ ⁺, C₁₂H₂₇—C₆H₄—SO₃—Na⁺, or combinationsthereof, and R_(f)′ is a perfluoroalkyl group having about 3 to about 18carbon atoms.